Covalent Organic Framework Electrocatalysts For Clean

PROGRESS REPORT
Covalent Organic Frameworks www.advmat.de
Covalent Organic Framework Electrocatalysts for Clean

Energy Conversion
Chun-Yu Lin, Detao Zhang, Zhenghang Zhao, and Zhenhai Xia*
of these noble metals hamper the com-

Covalent organic frameworks (COFs) are promising for catalysis, sensing, gas mercial use of the clean and sustainable
storage, adsorption, optoelectricity, etc. owning to the unprecedented combi- energy technologies.
nation of large surface area, high crystallinity, tunable pore size, and unique Extensive efforts and great progresses
molecular architecture. Although COFs are in their initial research stage, have been made toward the fabrication
of electrocatalysts with earth-abundant
progress has been made in the design and synthesis of COF-based electroca-
materials, including metals and their
talysis for the oxygen reduction reaction, oxygen evolution reaction, hydrogen compounds (e.g., perovskite oxides, 3d
evolution reaction, and CO2 reduction in energy conversion and fuel genera- transition metal oxides and dichalcoge-
tion. Design principles are also established for some of the COF materials nides, and metal alloys[6–20]), and metal-
toward rational design and rapid screening of the best electrocatalysts for a free carbon nanomaterials (e.g., gra-
phene, carbon nanotubes, nanoporous
specific application. Herein, the recent advances in the design and synthesis
carbon[7–10]). 2D covalent organic frame-
of COF-based catalysts for clean energy conversion and storage are pre- works (COFs) are an emerging class of
sented. Future research directions and perspectives are also being discussed molecular frameworks linked by covalent
for the development of efficient COF-based electrocatalysts. bonds. Although this COFs research field
is still in its infancy, the unprecedented
combination of large surface area, high
1. Introduction crystallinity, tunable pore size, and unique molecular architec-
ture has made COFs tantalizing targets for a new generation
The growing consumption of global energy from diminishing of electrocatalysts, photovoltaics, field-effect transistors, light-
traditional sources has posed serious challenges to environ- emitting diodes, selective transport, sensors, and drug delivery
mental protection and energy supplies. A promising solution systems.[11–13] COFs with precisely controllable structures can
to the challenges is to introduce clean and sustainable energy be constructed by selecting appropriate building blocks and
sources including electrochemical/photoelectrochemical water linkage motifs, providing an ideal material system for efficient
splitting for hydrogen fuel production, fuel cells for clean electrocatalysis. Recently, significant advances have been made
electricity generation, and batteries for clean energy storage. in the design and synthesis of COFs for efficient clean energy
These emerging energy technologies are under intensive R&D technologies. For example, COF-based catalysts have outper-
owning to their high efficiency, sustainability, and no pollution formed the best commercial catalyst, Pt, for catalyzing ORR in
or greenhouse gas emission.[1,2] Water splitting is believed to be terms of catalytic activity, long-term stability, and resistance to
a crucial technology for efficient sustainable energy generation CO-poisoning.[14] In this review, the principles, progress, and
and storage with fuel cells and metal–air batteries.[3,4] However, perspectives in COF material design, synthesis, and applica-
these clean energy technologies require noble metal catalysts tions are overviewed, and the future direction is discussed to
to promote key chemical reactions: oxygen reduction reaction develop efficient COF-based catalysts for clean energy conver-
(ORR), oxygen evolution reaction (OER), and hydrogen evolu- sion and storage.
tion reaction (HER). Currently, the state-of-the-art catalysts for
these chemical reactions are noble metals (e.g., Pt) or their
oxides (e.g., RuO2).[3,5] However, the high price and scarcity 2. Materials Design for COF-Based
Electrocatalysts
C.-Y. Lin, Dr. Z. Zhao, Prof. Z. H. Xia 2.1. Principles for Energy-Conversion Electrocatalysts
Department of Materials Science and Engineering
University of North Texas
Denton, TX 76203, USA Electrocatalysts are essential in key energy conversion reactions
E-mail: Zhenhai.xia@unt.edu such as ORR in fuel cells, OER in rechargeable metal–air bat-
D. Zhang, Prof. Z. H. Xia teries, HER in water splitting, CO2 reduction reaction (CRR) in
College of Energy artificial photosynthesis, and triiodide reduction reaction (IRR)
Beijing University of Chemical Technology
Beijing 100029, China
in dye-sensitized solar cells. In fuel cells, hydrogen is split into
its constituent electrons and protons on electrode (the anode).
DOI: 10.1002/adma.201703646 While the electrons flow out of the anode to form electric
Adv. Mater. 2017, 1703646 1703646 (1 of 16) © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de
current and end up at the cathode to reduce oxygen, the pro-

tons combine with the reduced oxygen species into water on the Chun-Yu Lin is a Ph.D.
cathode in acidic media. The ORR (O2 + 4H+ + 4e− → 2H2O) on candidate in the group of
cathode is a sluggish chemical process that determines the effi- Prof. Zhenhai Xia in the
ciency of the devices and needs catalysts to generate electricity. Department of Materials
In rechargeable metal–air batteries, ORR and OER occur in dis- Science and Engineering
charging and charging processes, respectively, and OER is the at the University of North
inverse reaction of ORR. In the discharge process of a metal–air Texas. His current scientific
battery, for example, mixed Li-air battery, metal (Li) is split into interests are carbon nano-
its constituent electrons and cations on the anode (Li → Li+ + materials, heterogeneous
e−).[15] While the electrons flow out of the anode to provide elec- catalysis, and the design
trical power and end up at the cathode to reduce oxygen, ORR principles of catalysts,
(O2 + 2H2O + 4e− → 4OH−) (similar to the reactions on cathode energy-conversion materials,
in a fuel cells in alkaline media), the Li+ ions diffuse through and energy-storage materials,
the electrolytes and then combine with the reduced oxygen which are related to fuel cells, metal–air batteries, and
species into soluble lithium hydroxides (LiOH) under a basic water splitting.
condition. In the charge process of the battery, OER (4OH− →
O2 + 2H2O + 4e−) occurs at the same cathode and Li+ ions dif- Detao Zhang is a Ph.D. candi-
fuse back to the anode. Water splitting is the major source of date at the Beijing University
clean hydrogen fuel, and it involves the dissociation of a water of Chemical Technology. In
molecule into its constituent parts: 2H2O → 2H2 + O2, which 2014 he obtained his bach-
is thermodynamically highly unfavorable. The reaction can elor’s degree, followed by his
be viewed as a combination of the OER (2H2O → O2 + 4H+ M.S. in molecular dynamics
+ 4e−) and the HER (2H+ + 2e− → H2), and thus the use of at the State Key Laboratory
appropriate OER and HER catalysts to reduce both overpoten- of Organic–Inorganic
tials is essential. In artificial photosynthesis, the critical reac- Composites. In 2016, he
tion is CO2 reduction. In principle, CO2 can be reduced to CO moved to the College of
(CO2 + 2H+ + 2e− → CO + H2O) or hydrocarbon products (e.g., Energy at Beijing University
CH4, HCO2H, CHOH, CH3OH, etc.).[16–18] With the sunlight of Chemical Technology to
utilized, this process also potentially represents energy routes pursue his Ph.D. His current
that combine renewable energy with CO2 reduction. However, work focuses on the theoretical study of carbon-based
transforming CO2 into CO or fuels by reduction is scientifically catalytic materials as oxygen-evolution- and oxygen-reduc-
challenging, requiring appropriate catalysts and energy input. In tion reaction catalysts.
a typical dye-sensitized solar cell (DSSC), there is an important
redox reaction, iodide/triiodide (I−/I3−) that mediates the cell.
The oxidized redox mediator, I3−, diffuses toward the counter
Zhenghang Zhao received
electrode and then it is reduced to I− ions (I3− + 2e− → 3I−) on
his Ph.D. in 2017 from the
counter electrode.[19,20] Overall, in all these energy systems, cata-
University of North Texas in
lysts are needed to promote the key chemical reactions to gen-
the group of Prof. Zhenhai
erate electricity, chemical products or fuels.
Xia. His research focuses
As electrocatalysts dominate the electrochemical perfor-
on multilevel computa-
mance of the energy-conversion devices, it is critical to design
tional materials science,
the electrocatalysts with high catalytic activities, low cost, and
heterogeneous catalysis,
long durability in acidic or alkaline media. Noble metals such
carbon nanomaterials, fuel
as Pt have been used as benchmark electrocatalysts in energy
cells, oxygen reduction and
storage and conversion for decades. As early as 1978, Miles
evolution reactions, and
et al. did the cyclic voltammetric studies on different metals and
design principles for the
their alloys, and found that they had equal performances for
development of novel catalysts for energy storage and
HER, but different for OER. RuO2 was the best electrocatalysts
conversion.
for OER in acidic environment,[21] while the best electrocatalysts
for ORR is Pt.[22] Theoretically, density functional theory (DFT)
has been used to calculate the reaction free energy, the adsorp-
tion energy, and the overpotential of the electrochemical reac-
tions. The OER overpotential of RuO2 is 0.42 V while the ORR due to corrosion and/or solvent effects. Thus, new catalysts
overpotential of Pt is 0.45 V.[23,24] Pt and RuO2 have become should be cost-effective, and have similar or higher catalytic
benchmark electrocatalysts for ORR and OER, respectively. activities than these benchmark electrocatalysts. Furthermore,
Nevertheless, the large-scale commercial use of noble metals as the catalysts should have a large surface area, good mechanical
electrocatalysts is hindered by (i) high cost which may comprise properties, and high electrical conduction. In most electrochem-
over 50% of the total cost of a fuel cell, and (ii) poor stability ical cells, such as fuel cells, ORR occurs under severe chemical
conditions, such as high electric potential (1 V/SHE) and high incorporation of the structures similar to those existing in the
hydrogen ion concentration (1 pH), in the cathode.[25] Under biomolecules could create new types of high performance non-
such severe electrochemical conditions, the catalysts alternative precious metal catalysts.[6] This provides an effective approach
to precious metals should be designed to resist electrochemical for designing inexpensive and durable electrochemical catalysts
corrosion in addition to high catalytic activities. for fuel cells, as well as biological applications.
2D COFs, based on covalently bonded rigid (conjugated) Currently, metal catalysts, such as Au, Fe, and Ni, have
structures, consist of porous and crystalline phases with excep- been used to catalyze various chemical process; they are often
tional thermal stabilities (up to 600 °C), low densities, and dispersed as particles on a support material, such as carbon,
large surface areas.[12] Compared to conventional materials oxide, zeolite, and so on. However, these metal particles tend
(e.g., polymer) energy conversion, the 2D COFs possess several to agglomerate and grow during the use, which causes their
inherent advantages for electrocatalysts, as follows. overall surface area to decrease, and consequently catalyst
activity to deteriorate.[29] Incorporating COFs with metal mac-
rocyclic clusters provides a new approach to use single-atom
2.1.1. Atomically Precisely Controlled 2D Structures metals in the catalysts with a highly homogeneous dispersion.
The metal-contained COFs show high efficiency and stability in
The ability to precisely control the heteroatom structures pro- catalytic environments.[30]
vides a powerful design approach to tailor the properties. The COFs also show some advantages over metal–organic frame-
construction principles for COFs enable atomically precise inte- works (MOFs) as electrocatalysts. In COFs, strong covalent
gration of building blocks to achieve predesigned compositions, bonds, instead of metal ions or clusters coordinated to organic
components, and functions. This allows us to design and syn- ligands in MOFs, are used to form the frameworks. Using the
thesize hierarchical nanoarchitectures with microchannels as strong covalent bonds to connect organic building blocks can
“highways” for ion diffusion and nanochannels as “shortcut” construct very stable ordered structures with designable pore
for ions to access active sites. Such nanoarchitectured mate- size, flexible molecular structure, and permanent porosity.
rials with precisely controlled channels/dopant locations and Because of their covalent bond connection, COFs have excep-
highly ordered network structure could significantly enhance tional thermal stabilities (up to 600 °C) while MOF materials
catalytic performance. Besides, conjugated 2D COFs could are unstable and easy to collapse at high temperature (up to
intrinsically exhibit low bandgaps and high charge mobilities, 350 °C).[31] In addition, the structures of MOFs are affected
attractive for optoelectronic and related energy devices.[26] In easily by the environments such as humidity.[32] Furthermore,
principle, precisely controlled 3D COF architectures could also while the catalytic activities of COFs can be enhanced by incor-
be synthesized based on 2D COFs, which provides an addi- porating metal macrocyclic units,[6,30] most MOF materials do
tional dimension for functionalization.[27] not possess high catalytic activities because the metal ions are
fully coordinated by the organic ligands. In order to improve
the catalytic activities, unsaturated coordinations of metal ions
2.1.2. Flexibility for Materials by Design have to introduce into the MOFs, but this can cause instability
of the structures and decomposition of pores.[33]
Apart from the precisely controllable frame structures, the Overall, COFs have emerged as a new class of porous mate-
well-defined pores can be used for reticular chemistry and post- rials, the molecular structure of which could be precisely
synthetic modification,[11,27,28] where complementary donor/ controlled through the selection of different building blocks
acceptor molecules could be inserted. This allows for the fabri- containing light elements such as C, B, N, and O.[7,40] The spe-
cation of versatile COFs with design-in units and functions. For cific surface areas of COFs exceeds those of well-known MOFs
example, COF structures can be adjusted by choosing the var- and zeolites.[34] Owning to their unique molecular structures,
ious R such as alkyl group, phenol group, and pyridine group, COFs could be designed to serve as an excellent electrocatalyst
and it is tunable by postsynthetic modification.[28] Moreover, for clean energy conversion and storage.
R group can be modified to allyl group or (CH2)11CH3 to replace
the arylboronic acid group in COF.[27] The postsynthetic modi-
fication is critical to extend COF functions by attaching func- 2.2. Synthesis of COFs
tional groups selected from a “gene pool” of chemical sources.
COFs are porous network polymers, which include cores and
linkers, synthesized via organic coupling reactions to form
2.1.3. Incorporation of Bioactive Macrocyclic Units strong covalent bonds between the basic units. The strongly
covalent bonds can be used to build the order structure with
One of advantages of the COFs as electrocatalysts is that they organic building block instead of the ionic bonds in MOFs. The
can be incorporated with transition metal macrocyclic clusters, porous organic frameworks linked by strong covalent bonds
including porphyrin, phthalocyanine, and tetraazaannulene. In were first synthesized by Yaghi and co-workers.[35] Later, Xu
some metal macrocyclic compounds, there is a core structure et al. proposed the triphenylbenzene dimethoxy terephthalde-
similar to a typical biounit, iron porphyrins in cytochrome c hyde covalent organic frameworks (TPB–DMTP–COF) that were
oxidase in blood cells. In Nature, these transition-metal macro- synthesized by organic linkers.[36] The multifunctional COFs can
cyclic units in biomolecules play a key role in achieving certain be prepared with different edge linkers.[36] The nature of huge
important biological functions. From biomimetic point of view, surface area, tunable structure, and relative derivative can create
COF-LZU1) (Figure 1h).[41] Postmodifica-

tion of the pore surface can also be achieved
through the “click” reaction to form the
functionalized COFs (Figure 1i).[28] Thus,
the molecular length of these building units
determines the pore size of COFs while their
shape controls the topology of the porous
structures.
The selected basic building blocks and
linkers will determine the structures of COFs
in designing 2D or 3D configuration. For
example, the linear building blocks will gen-
erate 2D COFs[42] and the tetrahedral building
blocks can be used to build 3D COFs.[40,43]
Rigid structures can then be formed due to
the π-electron moving along with building
block of aromatic system. For example, COF-
102 is made of tetrahedral building structure
by self-condensation and keeps pore size
cavity ≈5.66 Å.[44] The length of building
blocks will determine the pore size of struc-
tures. 2D COFs, such as porphyrin or phth-
Figure 1. Building blocks and linkers for construction of 2D and 3D COFs. a) linear building block
alocyanine, were made of the planar sheets
B2, that can connect with (b), (c), (d), (e), (f) for 2D COFs with different pore sizes[39] (repro- in 2D by π−π interaction to form the layer
duced with permission, copyright 2015, Royal Society of Chemistry), b) 120° building block for channel, and the 3D COFs were made of tri-
forming benzene-ring structure B3, c) 90° building block for 2D COFs BT, d) 90° building block angular and tetrahedral units, such as COF-
for 2D COF structure B4, e) 120° and 60° building block for 2D COF structure B4, f) 60° building 102,103,105, and 108.[44]
block for 2D COF structure B6, for building COF materials which are CuP–COF,[59] (reproduced The main synthetic methods for COFs
with permission, copyright 2012, Royal Society of Chemistry) 4PE-1P-COF,[146] (reproduced with
include microwave,[45–47] solvent heating,[35]
permission, copyright 2016, American Chemical Society) D-A COF,[59] (reproduced with per- [42]
mission, copyright 2012, Royal Society of Chemistry) star-shaped COF,[147] (reproduced with flow controlling, ionothermal,[48] mechan-
[49]
permission, copyright 2012, Royal Society of Chemistry) CAF,[148] (reproduced with permis- ical delamination, and surface media[50–52]
sion, copyright 2017, Nature Publishing Group) g) tetrahedrally structured building units for while the most common synthetic reactions
assembly of 3D COFs (e.g., COF-300) with linear building unit,[12,40] (reproduced with permis- are Schiff-base reaction,[40,53] cyclotrimeri-
sion, copyright 2009, American Chemical Society, and copyright 2012, Royal Society of Chem- zation,[48,54] and boronic-based condensa-
istry) h) building block for chemical and extended structures of COFs,[12,41] (reproduced with
tion.[35,44] The covalent bond formation is the
permission, copyright 2011, American Chemical Society, and copyright 2012, Royal Society of
Chemistry) and i) COF (N3-COF-5) and functional group for postmodification of the COF-pore key process in the above methods to prepare
surface via the “click” reaction to form the functionalized COFs.[28] (reproduced with permis- COFs via regulating the temperature, solvent,
sion, copyright 2011, Nature Publishing Group). flow speed, and thermodynamic equilibrium.
The secondary linkages molecules, which are
2D and 3D COFs for various preponderant applications such as hydrazones,[53] imines,[40] boroxines,[35] boronate ester,[35] and
energy conversion, light absorption, and emission.[37,38] triazines,[48] are rigid aromatic structures with porous materials,
COFs show the unique functions via offering the area for and are usually used in the synthesis of COFs. Thus, a COF can
interaction of electrons, photons, holes, and molecules. There- be designed and synthesized by selecting basic building blocks,
fore, the critical part of the rational design is how to design linkage molecules, and proper synthesis methods.
the useful space structures. The diversity of building blocks
can generate various COF materials for adjustable struc-
tural and functional application. As schematically shown in 2.3. General Design Principles of COFs for Electrocatalysts
Figure 1, there are six typical building blocks of 2D COFs:
linear building block B2, T-shaped building block BT, 1,3,5 There are three essential factors, activity, selectivity, and sta-
centrosymmetric building block B3, rhombus-shaped building bility, which need to be considered in the development of new
block B4a, cross-shaped building lock B4b, and 1,2,3,4,5,6 cen- catalysts. In particular, the activity is directly related to the
trosymmetric building block B6.[39] The linkage molecules exposed active sites on catalysts and is important to the rational
include the C, N, Cl, Br, I, N3, B(OH)2, CHO, OH, alkyl group, design of high-performance catalysts. Since the reactions occur
NH2, and thienyl group. The COFs with different architectures only on these active sites (active centers), the apparent activity
can be designed and synthesized by connecting the building for a solid catalyst is governed by the unit activity on each active
blocks with linkers via appropriate synthesis methods such as center (intrinsic), and the number of exposed active centers for
cross coupling or self-condensation. In addition, 3D COFs can a particular mass loading (extrinsic). Therefore, design princi-
be assembled from linear and tetrahedrally structured building ples can be established through the intrinsic and extrinsic fac-
units (Figure 1g)[40] or chemical and extended structures (e.g., tors for COF-based catalysts.
blocks with different shape. Mostly, the linking groups are all
rigid with a planar configuration like boroxines,[35] triazines,[48]
imines,[40] and hydrazones.[53] For an efficient configuration of
porous structure, building blocks with rigid aromatic moieties
are highly recommended. Hierarchy COF (Figure 2d) using
templates such as carbon nanotube, carbon nitride, and gra-
phene to provide the high active sites, large surface area, and
improved electrical properties.
Controlling structural regularity is another key issue in the
design and synthesis of efficient COF catalysts. According to
Thomas and co-workers, the structural regularity is not guaran-
teed in the synthesis of COFs. Amorphous porous materials will
be obtained when rigid but contorted building blocks are used
in the reactions.[48] In this case, design principles in crystal engi-
neering are also valid for those of crystalline COF materials.[55]
Finally, functional moieties are also essential in the design
of efficient COF catalysts. In addition to the functional groups
introduced in the reaction, postsynthesis can also be used to
introduce the functional moieties into the COF network through
coordinative incorporation and chemical transformation.[56]
Bottom-up approach is another strategy for synthesizing func-
Figure 2. COFs with four different structures, including a) metal-free,[59] tional COFs. In this method, the functional moieties are directly
reproduced with permission. Copyright 2012, Royal Society of Chemistry. incorporated into the building units before the synthesis of the
b) Heterometal,[100] c) hybrid,[149,150] and d) hierarchical porous config COFs. The homogeneous arrangement of the functional blocks
uration.[151] Reproduced with permission. Copyright 2013, 2014, and 2016, can maintain the chemical stability of the COFs. Thus, the fea-
American Chemical Society. tures of building blocks, including rigidity, shape, size and func-
tionality should be overall considered in the design of COF cata-
For a metal-free COF catalyst (Figure 2a), the intrinsic lysts. Besides, the synthetic reactions and optimal conditions also
factor, i.e., the unit activity, would be related to the heteroatoms need to be considered for the formation of crystalline COFs.[12]
(e.g., N, P, S, etc.) in COFs. These heteroatom dopants would Most COFs with π-conjugated organic structures are found
strongly affect the catalytic activities. Therefore, the design to show semiconducting behaviors, where the charge transport
strategy to enhance the catalytic activities is to select the best originates from the π–π interaction between the molecules in
dopants (or co-dopants) in COFs. For those COFs containing the solid state. On the other hand, π–π interaction is one of
metal ions (Figure 2b), e.g., porphyrin, the metals usually play the foremost driving forces for assembling π-conjugated mole-
a major role in catalyzing the reactions. The type and distribu- cules to form crystalline states.[11,57–61] Yaghi and co-workers[62]
tion of the metal ions as well as ligand structures determine selected porphyrin as units to create COFs (COF-366 and -66)
the efficiency of the COF catalysts. Hybrid systems (Figure 2c) with the highest charge carrier mobility values among known
can also be used to enhance the catalytic activities of active organic crystalline conducting polymers. These materials with
center through synergic effect between COF and matrix (e.g., the special structures display high photocatalytic activities for
graphene and carbon nanotube). In addition, hybrid nanostruc- photochemical HER in water spitting. Therefore, COFs can be
tures would improve the electron transfer by providing efficient modified to be excellent photocatalysts by changing the degree
conduction channel and more effective surface area. of conjugation in the ligands.
To increase the number of exposed active sites (an extrinsic Electron transfer is critical in electrochemical reactions such as
factor) in COFs for electrocatalysts, the basic principle is to ORR, OER, and CO2 reduction. To improve the electron transfer,
control pore size through the covalent bond formation of the COFs can be deposited on conductive supporting materials to
building units. COFs can be built with various types of rigid form hybrid systems (e.g., graphene and carbon nanotube). This
organic monomers with different chemical configurations.[12] hybridization is proved to be an efficient way to enhance the cata-
The predictable crystalline structures come from the diverse lytic activities due to the improved electric conductivity and the
synthetic organic reactions. In addition to chemical configu- synergic effect between COFs and the supporting materials.
rations, there are several main factors need to be considered An alternative way to improve the electric conductivity as
including porosity, structural regularity, and functionality, well as activities and high-temperature stability is to carbonize
which could increase the number of exposed active sites. the COFs after synthesis. As shown by Xiang et al.,[14] at high
Porosity is the first concern in making efficient COF cata- temperature (950 °C) the conjugated structures of C-COP-P
lysts. Most of the design of porous COF materials is to utilize are altered and new carbon nanostructures are formed with
the rigid building blocks to generate extended porous archi- the degree of graphitization depending on the treating tem-
tectures, in which the active centers could be accessed. The perature. Although the original COF structures are changed
pore size of COFs can be adjusted by introducing the building after the high temperature treatment, the main skeletons
units with different molecular length while the topology of of the COF materials remain the same as original ones after
the porous structures can be altered by selecting the building carbonization.[14] In addition, the active chemical compositions
(e.g., N, P, and S) distribute similarly as in the original struc- on the cathode are very slow without catalysts. Platinum can
tures. This provides a new approach to precisely control the greatly accelerate the ORR, with the four-electron pathway
materials microstructure even after pyrolysis. The resultant predominant in alkaline and acidic media.[72] Thus, those mate-
COF materials show high electrocatalytic activities and skeleton rials that promote four-electron process could serve as efficient
stability after carbonization.[30] catalysts to replace expensive platinum. The ORR paths are
During the course of OER, HER, and CRR activities, the gas surface-sensitive and the active sites for four-electron process
bubbles may be generated to cover the electrode surface or the require special structural, physical, and chemical properties.
pores of the COFs. This nonconducting phase apparently blocks COFs have been explored as electrocatalysts due to their unique
the active sites and the electrolyte diffusion, creates dead area, structures, large surface area, and tunable pore size. The COFs
and results in an impeded mass transfer process and compro- in their pristine state show good catalytic activities for ORR.
mised performance.[63,64] Although the disengagement process More often, the COFs are carbonized into graphene-like struc-
of gas bubbles can be promoted in certain degree by including tures with heteroatom dopants uniformly distributed in the
ultragravity[65] or ultrasonic treatment,[66] they are not cost-effec- graphene matrix, making the COFs even better for catalyzing
tive for industrial production. Using MoS2 thin film with nano- ORR. The pyrolysis of COFs has become an effective method
structured surface morphologies as electrodes for HER, Jiang in precisely controlling the type and distribution of dopants in
and co-workers showed a much higher current density increase carbon nanomaterials. Currently heteroatom (e.g., N) dopants
and stability than the flat one in overpotential range due to the are introduced into carbon nanomaterials (e.g., graphene)
in-time leaving of as-formed H2 bubbles.[67] Similar concept of either by in situ doping during the graphene synthesis,[7,77] or
underwater “superaerophobic” (i.e., low bubble adhesive) elec- postdoping of preformed graphene nanostructures by exposing
trode surface with nanoporous architecture could be introduced them to heteroatom-containing moieties.[78,79] However, none
into the design and fabrication of COF-based electrodes to solve of these heteroatom-doping methods can precisely control the
the bubble problem. For example, some superaerophobic func- locations of heteroatoms in the doped carbon nanostructures.
tional groups could be anchored to the COFs such that the gas Through carbonization of the COFs, the location and composi-
bubbles in the pores can be cut into a discontinuous state and tion of the dopant heteroatoms can be precisely controlled. This
finally leave the surface with ease. provides a new and powerful approach to tailor the structures
of heteroatom-doped graphene and other (carbon) nanomate-
rials to improve their catalytic activities.
3. Oxygen Electrocatalysis for Clean The COF-based metal-free electrocatalysts for ORR were first
synthesized by Xiang et al. using N-rich building blocks from
Energy Conversion
triazine derivatives through Yamamoto polycondensation reac-
ORR occurs in many important chemical reaction processes, tion.[30] These N-rich COFs were then treated at high tempera-
such as energy conversion (e.g., fuel cells, metal–air batteries, ture in an inert atmosphere to form N-doped graphitic carbon.
etc.), corrosion (e.g., electrochemical corrosion), and bio- Four COF graphene derivatives with varied N doping levels
processes (e.g., respiration).[68–71] For fuel cells, oxygen reduc- and porous structures were made with different N-containing
tion on cathode plays an essential role in producing electricity building blocks (Figure 3a–d). In the COF-based graphene deriv-
while OER occurs in water splitting or the recharging process atives, the exact N-dopant positions were controlled by control-
of the metal–air batteries.[72,73] Noble metal catalysts are usually ling the molecular structures of COF precursors. This approach
used in these devices to promote these key but sluggish chem- could be applied to graphitic carbon and its derivatives, doped by
ical reactions, and thus the catalysts determine the efficiency other heteroatoms (e.g., B, S, and P), with atomically precisely
of the devices. COFs as an alternatives material to the noble controlled locations. This well-controlled N-doped holey graphitic
metals are a new development in searching for efficient and carbon material shows the similar onset potential as the com-
cost-effective catalysts for ORR and OER. Since 2D COFs are mercial Pt/C catalyst, and the half-wave potential of the COF-
made of conjugated macromolecular structures that are similar based catalyst reaches 0.78 V, comparable to that of Pt/C (0.80 V).
to graphene, they can be synthesized by controlling functional The transferred electron number (n) is 3.90 per O2 molecule for
groups at the edge of pores for gas storage,[74–76] lithium bat- the COFs, very close to ideal four-electron transfer ORR.
teries, solar cells, and fuel cells.[36] Metal ions play a key role in diverse biological functions as
In ORR, a hydrogen molecule is split into two electrons and well as traditional catalysts. In natural photosynthesis, light
two protons on the anode in fuel cells. There are two possible harvesting, together with photoinduced charge separation
reaction pathways in ORR: i) two-electron transfer with the for- and catalysis modules capture solar energy and convert water
mation of hydrogen peroxide into oxygen, electrons, and protons (an intermediate form of
“hydrogen”) efficiently; these protons and electrons are then
O2 + (2H+ + 2e − ) → H2O2 (1) used to reduce CO2 to various organic compounds by biocata-

lysts.[80] In these processes, a key catalytic unit, water-oxidizing
and ii) four-electron process with water as a byproduct complex, is a manganese–calcium cluster that controls reac-
tion coordinates, proton movement, and water access.[81,82] The
O2 + (4H+ + 4 e − ) → 2H2O (2) Mn4/Ca cluster catalyzes the most effective anodic “electrolysis”

system known in Nature.[83,84] Some types of photosynthetic
in acidic environments. The four-electron transfer is more organisms possess a special enzyme, hydrogenase, either in
efficient than the two-electron one. The reduction processes iron nickel (FeNi) or all iron (FeFe) type, which can produce
Figure 3. Schematic representations of cross-coupling reaction synthesis of COFs from different N-rich COF precursors: a) tris(4-bromophenyl)
amine (TBA), b) 2,4,6-tris-(4-bromo-phenyl)-[1,3,5] triazine (TBT), c) (4′-bromo-biphenyl-4-yl)- porphyrine (TBBPP), and d) 2,4,6-tris (5-bromothiophen-
2-yl)-1,3,5-triazine (TBYT). Reproduced with permission.[30] Copyright 2014, Wiley-VCH.
9000 molecules of H2 per second and per enzyme molecule at Yamamoto reaction using various N-containing metal–organic
30 °C.[85] In other words, this highly evolved biocatalyst is so complexes (e.g., TM-N4 unit (Figure 4) similar to a base unit
efficient that one mole of hydrogenase could produce enough in natural photosynthesis).[14,30,74,96–98] The TM-N4 unit-incor-
H2 in 2 h to fill the liquid hydrogen tank of a space shuttle.[85] porated COFs were further carbonized to form COF-derived
On the other hand, cytochrome c oxidase in mitochondria con- graphene analogues with precisely controlled nitrogen and
tains an active center of iron(II)-porphyrin structure that effi- metal locations. The resultant materials served as efficient and
ciently catalyzes “ORR” within cellular organelles.[86,87] Other durable electrocatalysts for ORR in both alkaline and acid envi-
structures like hemoproteins, an Fe-perpherin cluster in blood ronments with no methanol-crossover/CO-poisoning effects.
cells, enables certain important functions in living processes, The Fe-COFs exhibit the similar onset potential (0.80 V), com-
such as gas transportation, gas detection, chemical catalysis, parable with the Pt-based catalyst (0.96 V) in both acid and alka-
and electron transfer.[88,89] Embedding these genetic biocatalytic line environments and the transferred electron number is close
groups into a proper matrix could create new efficient electro- to 4 for each oxygen molecule in ORR. Moreover, cyclic voltam-
catalysts for clean energy conversion applications (Figure 4). metric (CV) shows that the TM-COFs exhibit the higher poten-
One of the advantages of the COFs as electrocatalysts is that tials, which is 0.77 V vs. RHE than metal-free COFs, which is
they can be incorporated with transition metal (TM) macrocy- 0.49 V vs. RHE.[14] As a consequence, the TM-COFs exhibit
clic clusters, such as porphyrin,[90–92] phthalocyanine,[93,94] and outstanding electrocatalytic activities for ORR. This work high-
tetraazannulene.[95] These TM-based macrocyclic compounds lights that the COFs can be incorporated with genetic units to
contain a generic unit similar to Co-porphyrins in vitamin create a new class of effective catalysts for energy conversion.
B12 or Fe-porphyrins in blood cells. Since TM-based macro- Similar work was performed by Ma et al., which showed
cyclic units exist in many living systems, which are critical in that the π stacking of Co-COF planar exhibited the great cata-
maintaining biological functions, the use of similar biounit lytic potential for ORR with four-electron pathway in alkaline
structures with innate reactive sites in COFs could signifi- media.[34] Their results suggest that Co-COF has similar cur-
cantly enhance the performance of COF-based catalysts, and rent and potential with 20% platinum-based catalysts. Here, the
even introduce new functions. Thus, COFs incorporated with transition metal of cobalt plays a significant role in improving
generic biounits provide a biomimetic strategy for design of catalaytic activities of the COF during the ORR process.[34]
efficient and durable ORR catalysts by mimicking nature. Apart from high catalytic activities, the stability of the cata-
A class of 2D COFs with TM (e.g., Fe, Co, Mn)-incorporated lysts is also important to the energy devices. Although COFs
macrocycles (Figure 5) was prepared by a nickel-catalyzed have been showed to have high catalytic activities, one concern
Figure 4. Biological structures (Mg-porphyrin in chlorophyll in leaves, Fe-porphyrin in Heme in red blood cells, and Co-porphyrin in vitamin B12), a
generic biological unit (Metalloporphine), and COFs with the biological unit.
is the stability of organic ligand in alkaline/acidic media. Wu The above reactions are catalyzed to produce hydrogen
et al. proposed a template-free pyrolysis method for Co-COFs by various electrocatalysts and photocatalysts, such as
(containing transition metal with four coordinate nitrogen noble metals and alloys,[106–109] nonprecious metals com-
(TM-N4)) to solve the issue of losing metal-nitrogen coordinated pounds,[110–114] and other nonmetallic materials.[115–117] How-
during the hydrolysis process.[99] Their experimental results ever, the poor stability in water has limited most of them in
show that this catalyst has excellent catalytic activities and sta- large-scale use. Recently, Bhunia and co-workers synthesized
bility in acidic and alkaline solutions. The half-wave potentials a crystalline, quasi-2D COF (SB-PORPy-COF) (Figure 6a)
are −0.18 V vs. AgCl/Ag and 0.64 V vs. RHE while the electron through 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAP)
transfer number is 3.94.[99] Therefore, transition metal with and 1,3,6,8-tetrakis (4-formylphenyl) pyrene (TFFPy) under
four coordinate nitrogen (TM-N4) show high stability and cata- solvothermal condition.[118] This is the first metal-free COF-
lytic activity in ORR, as reported by other researchers.[100,101] based electrocatalyst for electrocatalytic hydrogen evolution.
The COF has moderately high surface area (≈869 m2 g−1) and
promising chemical and thermal stability. In the electrochem-
4. HER Catalysts for Hydrogen Production ical hydrogen evolution experiment, the COF was drop-casted
on a glassy carbon electrode and its catalytic activity for HER
One of the most promising renewable energy is hydrogen. was measured in 0.5 (m) H2SO4 solution. It was shown that
Hydrogen fuel can be produced from water splitting under vis- the new catalyst was efficient in catalyzing HER with a remark-
ible-light irradiation.[102–104] HER in acid and alkaline solutions ably low onset overpotential of ≈50 mV, which is the lowest
proceeds in two half-cell pathways.[105] In acid solution reported overpotential ever for any types of COFs (Figure 6b.)
in acidic solution.[118] After 500 cycles in the potential range
2H+ + 2e − → H2 (3) 0.2 to −0.5 V vs. RHE at a scan rate of 100 mV s−1, no loss of
activity was observed in terms of both onset potential and cur-
which can follow different reaction pathways: 2H+ + 2e−+ * → rent density at different potentials. Thus, COFs are promising
H* (Volmer), and H+ + e−+ H* → H2 (Heyrovsky) or 2H* → material system as HER electrocatalysts and will attract the
H2 + 2* (Tafel), where the star * refers to an active site on a researchers to find abundant scope of utility and applicability
catalyst. to understand the electrochemical aspects of COFs.
Figure 5. Molecular structures and catalytic activities of COF-based catalysts. a–c) Schematic diagrams of synthetic process for TM (Fe, Co, or Mn)-
COF, d) measured current density of COF-based electrode as a function of applied potential (RHE), and e) experiment for crossover of fuel molecules
and CO poisoning of TM-COF and Pt/C catalysts. Reproduced with permission.[14] Copyright 2014, Wiley-VCH.
COFs are semiconductors, the bandgap of which can be evolved hydrogen and long-range order reconvert suggests that
altered by changing the degree of conjugation in the ligands TFPT–COF/ Pt system is a promising catalyst for hydrogen
indicating the possibility for being photocatalysts. In fact, this production.
material has emerged as a potential photoactive material for Utilizing the superior physicochemical property of nano
their crystalline and stability, large surface areas, high porosity, particles, Banerjee and co-workers[122] combined a highly stable
and high efficiency of light capture.[119] Moreover, the charge COF that synthesized from 1,3,5-triformylphloroglucinol with
mobility on the surface of some COFs was enhanced owing to 2,5-dimethyl-p-phenylenediamine and then anchored CdS
the existence of π arrays compared with 1D or 3D polymers.[120] nanoparticles on the COF surface to form a hybrid system. The
In 2013, Jiang and co-workers first demonstrated a squar- large surface area of COFs can increase the catalytic activity of
aine-based COF as a photoactive material that could absorb CdS nanoparticles. To examine HER catalytic activities, they
the visible photons and trigger the activation of molecular used Pt as cocatalyst and lactic acid as sacrificial agent under
oxygen.[120] After that, Lotsch et al.[121] constructed the hydro- visible light. The results showed that the hydrogen production
lytically stable hydrazine-based COF from 1,3,5-tris-(4-formyl- was 128 µmol h−1 g−1 when using bulk CdS as a catalyst while
phenyl) triazine (TFPT) and 2,5-diethoxy-terephthalohydrazide the plain COF is 28 µmol h−1 g−1. Amazingly, when CdS–COF
(DETH) building blocks. The COF has a bandgap of 2.8 eV (99:1) served as the catalyst, the hydrogen production was up
with a pore diameter of 3.8 nm and a Brunauer–Emmett–Teller to 1320 µmol h−1 g−1, which is 10-fold better than that of bulk
(BET) surface area of 1603 m2 g−1. To examine the photocata- CdS. Among all the CdS–COF hybrids that they had used, CdS–
lytic behavior of the TFPT–COF, they used Pt as proton reduc- COF (90:10) was found to perform the superior photocatalytic
tion catalyst and ascorbic acid as sacrificial electron donor. activity with a H2 production of 3678 µmol h−1 g−1. However,
When the TFPT-COF/ Pt system was illuminated under vis- the hydrogen production decreased when the support matrix
ible light up to 3 d, the system can be sustaining in producing further added because of shielding effect. In the following three
hydrogen of 230 µmol h−1 g−1, suggesting that the COF was consecutive cycle, the CdS–COF (90:10) hybrid was found no
stable enough to catalyze the HER. In the experiment, as they deactivation. Their work proved that COF as catalytic merit
changed aqueous triethanolamine (TEOA) solution as sacrifi- improved the catalytic activity of deposited nanoparticles.
cial electron donor, the volume of evolved hydrogen was up to In 2015, Lotsch and co-workers[123] synthesized a series of 2D
1970 µmol h−1 g−1 in the first 5 h with a quantum efficiency azine-linked COFs (N0-COF, N1-COF, N2-COF, N3-COF) using
of 2.2%. They also proved that the H2 was from the water, not triphenylarylaldehydes with central aryl ring containing 0–3
the decomposition of the COF itself. During the photocatalysis, nitrogen atoms (N = 0 (phenyl), N = 1 (pyridyl), N = 2(pyrim-
the long-range order of PTFT–COF’s had lost, but the catalytic idyl) and N = 3 (triazine)) as building blocks (Figure 6c,d), the
activity still exist. However, the crystallinity can reconvert by bandgaps of which are 2.67, 2.68, 2.62, and 2.65 eV, respectively.
subjecting it to its initial synthesis conditions. This high rate They found that the porosity and crystalline increased with
Figure 6. Design and synthesis of the COF catalysts for hydrogen production. a) SB-PORPy COF, b) polarization curves for the hydrogen evolution reac-
tion on bare GC (blue), Vulcan (red), and SB-PORPy-COF (black) electrodes.[118] c) A tunable triphenylarene COF for photocatalytic HER. Replacing CH
by N atoms at the green dots changes the angle between central aryl and peripheral phenyl rings, which results in different planarity in the COF. d) Syn-
thesis of Nx–COFs from Nx–aldehydes and hydrazine. e) The amount of hydrogen produced over 8 h using Nx–COF-based photocatalyst in the presence
of triethanolamine as sacrificial electron donor. f) Photonic efficiency (PE) of the COFs at different central wavelengths (CWLs). (a) and (b) reproduced
with permission.[118] Copyright 2017, American Chemical Society. (c) to (f) reproduced with permission.[123] Copyright 2015, Nature Publishing Group.
increasing the N atom content from N0-COF to N3-COF. In the H2 yield from N0-COF to N3-COF was 23 to 1703 µmol h−1 g−1,
hydrogen evolution experiments, Pt was used as cocatalyst and respectively (Figure 6e). By theoretical calculation they proved
TEOA as sacrificial electron donor. After 8 h test, the average that the improved stabilization of the radical anions in the
high nitrogen-containing COF matched the general trend in order to optimize this carbon dioxide catalytic platform, they
hydrogen generation. The stabilization of the anion radical may synthesized several expanded derivatives with large pore size
enhance the charge separation, and consequently increases and introduced building unit heterogeneity through a multivar-
the probability of effective electron migration to Pt cocatalyst. iate approach.[131] The results suggested that the heterogeneity
Since the photocatalytic test lasted up to 48 h, the amount of of the systems promoted the reduction of carbon dioxide to
hydrogen produced indicated that the hydrogen was gener- carbon monoxide with remarkably high activity and selectivity.
ated from the water not the decomposition of the COFs. The This work shows that compared with other frameworks, the
analysis of Nx-COF after the photocatalytic test suggested that exceptional structure allows the reactants to be in high contact
no obvious change in structure. Furthermore, after 120 h pho- with the catalytic active sites and strengthen the mass transfer
tocatalytic test, the N3-COF showed continuous hydrogen evo- of the reactants or products, thus enhancing the catalytic activity
lution and kept its structures stable in long-range order. Their of the COFs. It is expected that more unique structures of COF
work demonstrates that the COFs are potential in solar energy derivatives be synthetized, which may boost the efficiency for
conversion such as water splitting through visible light. Never- carbon dioxide reduction.
theless, since the quantum efficiency (QE) is below 5% (Figure
6f),[123] there is still a large space for the researchers to promote
their catalytic activity by optimizing the COFs. 6. Computational Approaches for Design and
Screening of COF Electrocatalysts
5. CO2 Reduction As discussed above, COFs are appealing for catalytic applica-
tions because of their tunable molecular architectures that
Carbon dioxide (CO2) is a greenhouse gas; it is of interest to could be rationally designed and precisely controlled to gain
transform carbon dioxide into valuable carbon-based prod- large surface area and excellent electronic structures to enhance
ucts. Through the reduction of CO2, various chemicals can catalytic activities.[4–6] Furthermore, reticular chemistry and
be obtained, including formic acid (HCOOH), or formate postsynthetic modification can effectively adjust the structures
(HCOO−) in alkaline media, oxalic acid (H2C2O4), or oxalate of COFs to facilitate ORR, OER, and HER. Although the cata-
(C2O42−) depending on solution pH, carbon monoxide, formal- lytic capabilities of COFs have been confirmed, most of the cata-
dehyde (CH2O), ethanol (CH3CH2OH), ethylene (CH2CH2), lysts are usually developed after a large number of experiments
methane (CH4), and many others.[124] Electrolytic approach is through trial-and-error approaches. A rational design via com-
a promising way to produce these chemicals and fuels for it putational approaches would significantly reduce the research
uses water as the reaction medium and it is easy to get, abun- expense and cut the research time. To this end, design princi-
dant and environmentally friendly.[125,126] The most widely ples for COF-based catalysts must be established to understand
employed electrocatalysts for CO2 conversion are metal-related which intrinsic material characteristics, or descriptors, control
materials.[127–130] However, some of them are unstable and catalysis and how the descriptor correlates the structures to the
easy to degrade in water, which limits their use in aqueous catalytic activity of COF-based catalysts.
medium. First-principle calculation provides an alternative approach
Recently, it was reported COF derivatives served as effec- to explore the molecular structures and catalytic properties of
tive electrocatalysts to reduce the carbon dioxide to carbon COFs. Theoretical investigation complements experiments, in
monoxide.[76] Chang and co-workers[76] prepared a Co-based particular when it is difficult or impossible for the experiments
COF (COF-366-Co) as an electrocatalyst to reduce CO2 to to characterize reaction intermediates.[132] Recently, novel 1D
carbon monoxide in aqueous solutions. The Co-COF was and 2D π-conjugated COF materials were designed on the basis
prepared via the imine condensation of 5,10,15,20-tetrakis of DFT techniques, and demonstrated that the bandgap was
(4-aminophenyl)porphinato cobalt [Co(TAP)] with terephthal- much smaller than that for the 1D conjugated polymers.[26] The
dehyde (BDA) (Figure 7). The activated COF material was calculation clearly indicates that there is a fundamental differ-
then deposited on porous conductive carbon fabric. The elec- ence in designing 1D and 2D semiconducting polymers, which
trolytes were carried out in carbon dioxide-saturated aqueous provides a design approach for functional COFs through “com-
bicarbonate buffer (pH 7.3) under applied potentials ranging putational bandgap engineering.”
from −0.57 to −0.97 V (vs. RHE). Only carbon monoxide was Through the first-principle calculations, several intrinsic
observed as the detectable carbon-based product. When the activity descriptors have been found, for example, the energy
potential was −0.67 V, the catalyst displayed the best perfor- level of a metal atom’s d-band center for metal surfaces,[133] and
mance. Carbon monoxide evolution was promoted by COF- eg filling energy for transition-metal-oxide perovskites.[134] For
366-Co at an initial current density of 5 mA mg−1, and the metal-free carbon-based catalysts (e.g., graphene, carbon nano-
Faradaic efficiency (FECO) of the catalysts (≈80 mA mg−1 cobalt) tubes), a characteristic of dopant, namely the product of elec-
is 90%. The catalytic process lasted up to 24 h, yielding more tronegativity and electric affinity of dopants, was identified as an
than 36 mL carbon monoxide (STP, equivalent to 1.6 mmol) activity descriptor for predicting ORR/OER activities, resulting
per mg COF. Scanning electron microscopy (SEM) showed that in a volcano relationship that predict the best carbon-based cat-
neither noticeable change in crystallinity and morphology nor alyst for ORR/OER.[135] For codoping, the same descriptor was
evidence of cobalt nanoparticles formation was found after the applied, yielding an inverted volcano relationship.[136] These
electrocatalysis test. When the hybrid catalyst system cycled at descriptors follow the well-known Sabatier principle, but give
least five times, the activity and selectivity did not decrease. In quantitative predictions for the best catalysts that locate at the
Figure 7. Design and synthesis of metalloporphyrin-derived 2D COFs for CO2 reduction. Reproduced with permission.[76] Copyright 2015, AAAS.
top of the volcanoes. These descriptors provide a powerful tool structure, and used it as a descriptor for TM–COFs. The rela-
to screen the best catalysts by guiding the experiments to climb tionship between the overpotential and the CFSE shows the
the volcanoes. volcano plots for 4e− reactions and 2e− reactions (Figure 8c,d).
For COF materials (Figure 8a), Lin et al. studied the catalytic Thus, CFSE is valid for both direct and indirect pathways.
behaviors of transition metal (TM)–COFs for catalyzing OER The mechanism map can divided into two regimes: (i) 4e−
and ORR via DFT calculations.[100] The overpotential of TM– reactions transfer (CFSE < 0), and (ii) 2e− reactions transfer
COFs was calculated to predict the catalytic activities of these (CFSE > 0). The FeCOF is identified to be the most efficient
materials. The overpotential forms a volcano shape when the catalyst among TM–COFs for ORR and OER.
adsorption energies ∆GO∗ − ∆GOH∗ and ∆GOH
0 0 0
∗ are applied The orbital energy-based descriptors are not only used to pre-
to correlate with overpotentials of the TM–COFs in OER and dict the best catalyst in the TM–COF materials system for energy
ORR, respectively (Figure 8b).[100] Although the adsorption conversion but are also used to predict the best COF-based cat-
energy as a descriptor well describes the catalytic behaviors alysts for the formation of hydrogen peroxide (H2O2). It is well
of electrocatalysts for OER and ORR, it does not correlate the known that H2O2 is a green chemical oxidant (with oxygen and
materials structures with the catalytic activities, and is thus water as only byproducts) as well as a potential energy carrier. Tra-
inconvenient to use it to screen the catalysts from numerous ditionally, H2O2 is produced through the anthraquinone process,
COF candidates. a batch method conducted in large-scale facilities. Compared to
Lin et al. proposed to use the crystal field stabilization the traditional energy-intensive process, the electroreduction of
energy (CFSE) as the descriptor to predict the best electro- oxygen to H2O2 in a fuel cell would be appealing for on-site pro-
catalysts for OER/ORR activities of various TM–COFs. The duction with very high efficiency. However, noble metals (Pd) are
CFSE is related to the d-orbital of transition metals and the needed to catalyze the ORR process. Based on the experimental
energy based on the bonding structures with the Jahn–Teller value of the free energy for hydrogen peroxide in 2e− transfer
effect.[137,138] This descriptor is determined by ligand struc- procedure,[141] it was predicted that hydrogen peroxide could be
tures on the transition metals and the orbital splitting such as produced directly with Zn- and Cu-COF catalysts. The COF-based
the split energy level between the t2g and eg for certain ligand catalysts could replace the noble metal catalysts in the electro-
structures.[138–140] In the original paper, the CFSE was calcu- chemical cells, making H2O2 production commercially viable.
lated based on square pyramidal ligand structures. We have To search for the effective catalysts for direct production
recalculated the CFSE using relatively simple square planar of H2O2, the catalytic activities of the alkaline-earth metal
Figure 8. a) Schematic of a TM-COF (TM = 3d transition metals). The green, blue, deep gold, and silver colors represent C, N, TM, and H, respectively.
b) Volcano plots of ORR overpotential (catalytic activities) against descriptors (adsorption energy of HO) and reaction pathways. c) OER and ORR
overpotentials as a function of CFSE for TM-COFs in four-electron reactions. d) ORR overpotentials as a function of CFSE and CE for TM and AM-COFs
in 2e−/4e− electron reactions. Reproduced with permission.[100] Copyright 2017, Wiley-VCH.
(Be, Mg, Ca, Sr, and Ba) contained COFs were also predicted and functions via atomically precise integration of building
using the DFT methods. Through the calculations of overpo- blocks. Thus, compared to conventional materials (e.g.,
tentials for 2e− and 4e− ORR, it was shown that alkaline-earth polymer) for electrocatalysts, the 2D COFs possess several
metal COFs prefer 2e− ORR with the product of H2O2. For inherent advantages including: (i) Atomically precisely con-
the rational design of a high-performance catalyst to generate trolled 2D structures that allow for tailoring the nanoporous
H2O2, a new descriptor, orbital configuration energy (CE)[142] architectures for optimizing catalytic performance; (ii) Comple-
(Figure 8d), was found to describe well the catalytic activities mentary donor/acceptor molecules could be inserted into COFs
of alkaline-earth metal-COFs. The 2e- transfer catalytic activity for reticular chemistry and post-synthetic modification, and
shows a volcano relationship with the descriptor. At the top of (iii) Incorporation of macrocyclic units for high performance
the volcano, the lowest overpotentials are 0.27 V for Ca-COF, nonprecious-metal ORR catalysts.
and 0.29 V for Sr-COFs, comparable to that of Pt (0.24 V).[143] Advance has been made in design and synthesis of COFs as
Alkaline-earth metal-COFs, in particular Ca- and Sr-COFs, have efficient electrocatalysts for OER, ORR, HER, and CO2 reduc-
been identified to be the most efficient catalysts for the direct tion in energy conversion and storage. Both metal-free and
synthesis of H2O2 via the electrochemical approach. nonprecious metal COFs were synthesized, and subsequent
carbonization of the COFs were also carried out to form COF-
derived graphene analogues. The COF catalysts served as
7. Summary and Future Directions effective and durable electrocatalysts for ORR in both alkaline
and acid environments without any methanol-crossover/CO-
COFs are an emerging class of framework materials with pre- poisoning effects. The COF materials were also demonstrated
cisely controlled pore size and topology, promising for a new to have the potential in solar energy conversion such as water
generation of electrocatalysts, photovoltaics, field-effect tran- splitting through visible light, and in the reduction of CO2, to
sistors, light-emitting diodes, selective transport, sensors, and transform this greenhouse gas into various chemicals or fuels.
drug delivery systems. The construction principles for this Design principles were established for some of COF-
material can achieve predesigned compositions, components, based electrocatalysts for ORR and OER on the base of the
first-principle calculations. An activity descriptor, derived from the open program (oic-201701001) of State Key Laboratory of Organic-
orbital energy and bonding structures, is identified, which Inorganic Composites at BUCT.
correlates COF structures with their catalytic activities. The
calculations also predict that alkaline-earth metal-porphyrin
COFs could catalyze the direct production of H2O2, a green Conflict of Interest
oxidizer. Among a series porphyrin contained COF structure The authors declare no conflict of interest.
with TM-COF (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn),
Fe and Co-COF show the best ORR and OER, which are com-
parable to Pt and RuO2. These predictions are supported by
experimental data, and the design principles derived from the
Keywords
descriptors provide an approach for rational design of new elec- covalent organic frameworks, electrocatalysts, energy conversion, energy
trocatalysts for both clean energy conversion and green oxidizer storage
production.
Received: June 30, 2017
Although progress has been made, this field of research is
Revised: August 14, 2017
still in its infancy. Looking forward, a future direction would be Published online:
to fully make use of construction principles for COFs to atomi-
cally precisely integrate building blocks to achieve predesigned
compositions, components, and functions. This would allow us
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Covalent Organic Framework Electrocatalysts for Clean

of these noble metals hamper the com-

current and end up at the cathode to reduce oxygen, the pro-

COF-LZU1) (Figure 1h).[41] Postmodifica-

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